Bright Infrared‐to‐Ultraviolet/Visible Upconversion in Small Alkaline Earth‐Based Nanoparticles with Biocompatible CaF 2 Shells
Abstract
Abstract Upconverting nanoparticles (UCNPs) are promising candidates for photon‐driven reactions, including light‐triggered drug delivery, photodynamic therapy, and photocatalysis. Herein, we investigate the NIR‐to‐UV/visible emission of sub‐15 nm alkaline‐earth rare‐earth fluoride UCNPs (M 1− x Ln x F 2+ x , MLnF) with a CaF 2 shell. We synthesize 8 alkaline‐earth host materials doped with Yb 3+ and Tm 3+ , with alkaline‐earth (M) spanning Ca, Sr, and Ba, MgSr, CaSr, CaBa, SrBa, and CaSrBa. We explore UCNP composition, size, and lanthanide doping‐dependent emission, focusing on upconversion quantum yield (UCQY) and UV emission. UCQY values of 2.46 % at 250 W cm −2 are achieved with 14.5 nm SrLuF@CaF 2 particles, with 7.3 % of total emission in the UV. In 10.9 nm SrYbF:1 %Tm 3+ @CaF 2 particles, UV emission increased to 9.9 % with UCQY at 1.14 %. We demonstrate dye degradation under NIR illumination using SrYbF:1 %Tm 3+ @CaF 2 , highlighting the efficiency of these UCNPs and their ability to trigger photoprocesses.
- Authors:
-
[1];
[1]
- Department of Materials Science and Engineering Stanford University 496 Lomita Mall Stanford CA 94305 USA
- Materials Science Division Lawrence Berkeley National Laboratory Berkeley CA 94720 USA, Department of Chemistry University of California, Berkeley Berkeley CA 94720 USA, Department of Materials Science and Engineering University of California, Berkeley Berkeley CA 94720 USA, Kavli Energy Nanoscience Institute Berkeley CA 94720 USA
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1786193
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition) Journal Volume: 59 Journal Issue: 48; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
Fischer, Stefan, Siefe, Chris, Swearer, Dayne F., McLellan, Claire A., Alivisatos, A. Paul, and Dionne, Jennifer A. Bright Infrared‐to‐Ultraviolet/Visible Upconversion in Small Alkaline Earth‐Based Nanoparticles with Biocompatible CaF 2 Shells. Germany: N. p., 2020.
Web. doi:10.1002/anie.202007683.
Fischer, Stefan, Siefe, Chris, Swearer, Dayne F., McLellan, Claire A., Alivisatos, A. Paul, & Dionne, Jennifer A. Bright Infrared‐to‐Ultraviolet/Visible Upconversion in Small Alkaline Earth‐Based Nanoparticles with Biocompatible CaF 2 Shells. Germany. https://doi.org/10.1002/anie.202007683
Fischer, Stefan, Siefe, Chris, Swearer, Dayne F., McLellan, Claire A., Alivisatos, A. Paul, and Dionne, Jennifer A. Wed .
"Bright Infrared‐to‐Ultraviolet/Visible Upconversion in Small Alkaline Earth‐Based Nanoparticles with Biocompatible CaF 2 Shells". Germany. https://doi.org/10.1002/anie.202007683.
@article{osti_1786193,
title = {Bright Infrared‐to‐Ultraviolet/Visible Upconversion in Small Alkaline Earth‐Based Nanoparticles with Biocompatible CaF 2 Shells},
author = {Fischer, Stefan and Siefe, Chris and Swearer, Dayne F. and McLellan, Claire A. and Alivisatos, A. Paul and Dionne, Jennifer A.},
abstractNote = {Abstract Upconverting nanoparticles (UCNPs) are promising candidates for photon‐driven reactions, including light‐triggered drug delivery, photodynamic therapy, and photocatalysis. Herein, we investigate the NIR‐to‐UV/visible emission of sub‐15 nm alkaline‐earth rare‐earth fluoride UCNPs (M 1− x Ln x F 2+ x , MLnF) with a CaF 2 shell. We synthesize 8 alkaline‐earth host materials doped with Yb 3+ and Tm 3+ , with alkaline‐earth (M) spanning Ca, Sr, and Ba, MgSr, CaSr, CaBa, SrBa, and CaSrBa. We explore UCNP composition, size, and lanthanide doping‐dependent emission, focusing on upconversion quantum yield (UCQY) and UV emission. UCQY values of 2.46 % at 250 W cm −2 are achieved with 14.5 nm SrLuF@CaF 2 particles, with 7.3 % of total emission in the UV. In 10.9 nm SrYbF:1 %Tm 3+ @CaF 2 particles, UV emission increased to 9.9 % with UCQY at 1.14 %. We demonstrate dye degradation under NIR illumination using SrYbF:1 %Tm 3+ @CaF 2 , highlighting the efficiency of these UCNPs and their ability to trigger photoprocesses.},
doi = {10.1002/anie.202007683},
journal = {Angewandte Chemie (International Edition)},
number = 48,
volume = 59,
place = {Germany},
year = {Wed Sep 23 00:00:00 EDT 2020},
month = {Wed Sep 23 00:00:00 EDT 2020}
}
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1002/anie.202007683
https://doi.org/10.1002/anie.202007683
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Near-Infrared Light-Triggered Dissociation of Block Copolymer Micelles Using Upconverting Nanoparticles
journal, December 2011
- Yan, Bin; Boyer, John-Christopher; Branda, Neil R.
- Journal of the American Chemical Society, Vol. 133, Issue 49
NIR-Triggered Anticancer Drug Delivery by Upconverting Nanoparticles with Integrated Azobenzene-Modified Mesoporous Silica
journal, March 2013
- Liu, Jianan; Bu, Wenbo; Pan, Limin
- Angewandte Chemie International Edition, Vol. 52, Issue 16
Relation between Excitation Power Density and Er 3+ Doping Yielding the Highest Absolute Upconversion Quantum Yield
journal, December 2014
- Fischer, Stefan; Fröhlich, Benjamin; Krämer, Karl W.
- The Journal of Physical Chemistry C, Vol. 118, Issue 51
Photoisomerization of Azobenzene Derivatives in Nanostructured Silica
journal, December 2006
- Sierocki, Paul; Maas, Huub; Dragut, Patrick
- The Journal of Physical Chemistry B, Vol. 110, Issue 48
Stimuli-Responsive Nanomaterials for Biomedical Applications
journal, February 2015
- Blum, Angela P.; Kammeyer, Jacquelin K.; Rush, Anthony M.
- Journal of the American Chemical Society, Vol. 137, Issue 6
Quantum Yields, Surface Quenching, and Passivation Efficiency for Ultrasmall Core/Shell Upconverting Nanoparticles
journal, March 2018
- Würth, Christian; Fischer, Stefan; Grauel, Bettina
- Journal of the American Chemical Society, Vol. 140, Issue 14
Small Alkaline-Earth-based Core/Shell Nanoparticles for Efficient Upconversion
journal, April 2019
- Fischer, Stefan; Mehlenbacher, Randy D.; Lay, Alice
- Nano Letters, Vol. 19, Issue 6
Lanthanide-Doped LiLuF 4 Upconversion Nanoprobes for the Detection of Disease Biomarkers
journal, January 2014
- Huang, Ping; Zheng, Wei; Zhou, Shanyong
- Angewandte Chemie, Vol. 126, Issue 5
Photocleavage of o-nitrobenzyl ether derivatives for rapid biomedical release applications
journal, August 2006
- Kim, Moon Suk; Diamond, Scott L.
- Bioorganic & Medicinal Chemistry Letters, Vol. 16, Issue 15
Ultraviolet light-mediated drug delivery: Principles, applications, and challenges
journal, December 2015
- Barhoumi, Aoune; Liu, Qian; Kohane, Daniel S.
- Journal of Controlled Release, Vol. 219
Self-assembly of upconversion nanoclusters with an amphiphilic copolymer for near-infrared- and temperature-triggered drug release
journal, January 2016
- Yan, Kai; Chen, Min; Zhou, Shuxue
- RSC Advances, Vol. 6, Issue 88
Small and Bright Lithium-Based Upconverting Nanoparticles
journal, September 2018
- Cheng, Ting; Marin, Riccardo; Skripka, Artiom
- Journal of the American Chemical Society, Vol. 140, Issue 40
Maßgeschneiderte Aufwärtskonvertierungsnanopartikel zur Detektion von Proteinwechselwirkungen in lebenden Zellen
journal, August 2016
- Drees, Christoph; Raj, Athira Naduviledathu; Kurre, Rainer
- Angewandte Chemie, Vol. 128, Issue 38
Yb3+ and Tm3+ concentration-dependent structural and optical properties of hexagonal NaGdF4 nanocrystals
journal, April 2014
- Noculak, Agnieszka; Fhui, Yong Shiew; Banski, Mateusz
- Journal of Nanoparticle Research, Vol. 16, Issue 5
Near-Infrared Photoregulated Drug Release in Living Tumor Tissue via Yolk-Shell Upconversion Nanocages
journal, September 2013
- Zhao, Lingzhi; Peng, Juanjuan; Huang, Qi
- Advanced Functional Materials, Vol. 24, Issue 3
Upconversion nanoparticles as versatile light nanotransducers for photoactivation applications
journal, January 2015
- Idris, Niagara Muhammad; Jayakumar, Muthu Kumara Gnanasammandhan; Bansal, Akshaya
- Chemical Society Reviews, Vol. 44, Issue 6
Near-Infrared-Triggered Azobenzene-Liposome/Upconversion Nanoparticle Hybrid Vesicles for Remotely Controlled Drug Delivery to Overcome Cancer Multidrug Resistance
journal, August 2016
- Yao, Chi; Wang, Peiyuan; Li, Xiaomin
- Advanced Materials, Vol. 28, Issue 42
Power dependence of upconversion luminescence in lanthanide and transition-metal-ion systems
journal, February 2000
- Pollnau, M.; Gamelin, D. R.; Lüthi, S. R.
- Physical Review B, Vol. 61, Issue 5
Efficient photocatalytic degradation of organics diluted in water and air using TiO 2 designed with zeolites and mesoporous silica materials
journal, January 2011
- Kuwahara, Yasutaka; Yamashita, Hiromi
- J. Mater. Chem., Vol. 21, Issue 8
Lanthanide-doped upconverting luminescent nanoparticle platforms for optical imaging-guided drug delivery and therapy
journal, May 2013
- Shen, Jie; Zhao, Liang; Han, Gang
- Advanced Drug Delivery Reviews, Vol. 65, Issue 5
Nanopartikel für die Aufwärtskonversion
journal, May 2011
- Haase, Markus; Schäfer, Helmut
- Angewandte Chemie, Vol. 123, Issue 26
Structural absorption by barbule microstructures of super black bird of paradise feathers
journal, January 2018
- McCoy, Dakota E.; Feo, Teresa; Harvey, Todd Alan
- Nature Communications, Vol. 9, Issue 1
Lanthanide-Based Heteroepitaxial Core–Shell Nanostructures: Compressive versus Tensile Strain Asymmetry
journal, October 2014
- Johnson, Noah J. J.; van Veggel, Frank C. J. M.
- ACS Nano, Vol. 8, Issue 10
Engineered Upconversion Nanoparticles for Resolving Protein Interactions inside Living Cells
journal, August 2016
- Drees, Christoph; Raj, Athira Naduviledathu; Kurre, Rainer
- Angewandte Chemie International Edition, Vol. 55, Issue 38
Drug delivery with upconversion nanoparticles for multi-functional targeted cancer cell imaging and therapy
journal, February 2011
- Wang, Chao; Cheng, Liang; Liu, Zhuang
- Biomaterials, Vol. 32, Issue 4
Explaining the influence of dopant concentration and excitation power density on the luminescence and brightness of β-NaYF4:Yb3+,Er3+ nanoparticles: Measurements and simulations
journal, June 2019
- Kaiser, Martin; Würth, Christian; Kraft, Marco
- Nano Research, Vol. 12, Issue 8
Ultra-small BaGdF5-based upconversion nanoparticles as drug carriers and multimodal imaging probes
journal, February 2014
- Yang, Dongmei; Dai, Yunlu; Liu, Jianhua
- Biomaterials, Vol. 35, Issue 6
Synthesis and Optical Properties of KYF 4 /Yb, Er Nanocrystals, and their Surface Modification with Undoped KYF 4
journal, October 2008
- Schäfer, Helmut; Ptacek, Pavel; Zerzouf, Otmane
- Advanced Functional Materials, Vol. 18, Issue 19
Energy-Cascaded Upconversion in an Organic Dye-Sensitized Core/Shell Fluoride Nanocrystal
journal, October 2015
- Chen, Guanying; Damasco, Jossana; Qiu, Hailong
- Nano Letters, Vol. 15, Issue 11
NaYF 4 :Yb,Er/NaYF 4 Core/Shell Nanocrystals with High Upconversion Luminescence Quantum Yield
journal, June 2018
- Homann, Christian; Krukewitt, Lisa; Frenzel, Florian
- Angewandte Chemie International Edition, Vol. 57, Issue 28
Sub-10 nm Hexagonal Lanthanide-Doped NaLuF 4 Upconversion Nanocrystals for Sensitive Bioimaging in Vivo
journal, November 2011
- Liu, Qian; Sun, Yun; Yang, Tianshe
- Journal of the American Chemical Society, Vol. 133, Issue 43
Colour-optimized quantum yields of Yb, Tm Co-doped upconversion nanocrystals
journal, February 2019
- Kraft, Marco; Würth, Christian; Palo, Emilia
- Methods and Applications in Fluorescence, Vol. 7, Issue 2
High-Resolution Fluorescence Diffuse Optical Tomography Developed with Nonlinear Upconverting Nanoparticles
journal, May 2012
- Xu, Can T.; Svenmarker, Pontus; Liu, Haichun
- ACS Nano, Vol. 6, Issue 6
Rare-Earth Nanoparticles with Enhanced Upconversion Emission and Suppressed Rare-Earth-Ion Leakage
journal, April 2012
- Wang, Ye-Fu; Sun, Ling-Dong; Xiao, Jia-Wen
- Chemistry - A European Journal, Vol. 18, Issue 18
Upconverting Nanoparticles
journal, May 2011
- Haase, Markus; Schäfer, Helmut
- Angewandte Chemie International Edition, Vol. 50, Issue 26
Optimal Sensitizer Concentration in Single Upconversion Nanocrystals
journal, April 2017
- Ma, Chenshuo; Xu, Xiaoxue; Wang, Fan
- Nano Letters, Vol. 17, Issue 5
Magnetogenetic Control of Protein Gradients Inside Living Cells with High Spatial and Temporal Resolution
journal, April 2015
- Etoc, Fred; Vicario, Chiara; Lisse, Domenik
- Nano Letters, Vol. 15, Issue 5
An enhanced energy migration strategy in upconverting nanocrystals: color-tuning with high quantum yield
journal, January 2019
- Hudry, Damien; Busko, Dmitry; Popescu, Radian
- Journal of Materials Chemistry C, Vol. 7, Issue 24
Upconversion Nanoparticles: Design, Nanochemistry, and Applications in Theranostics
journal, March 2014
- Chen, Guanying; Qiu, Hailong; Prasad, Paras N.
- Chemical Reviews, Vol. 114, Issue 10
Colloidal Tm 3+ /Yb 3+ -Doped LiYF 4 Nanocrystals: Multiple Luminescence Spanning the UV to NIR Regions via Low-Energy Excitation
journal, October 2009
- Mahalingam, Venkataramanan; Vetrone, Fiorenzo; Naccache, Rafik
- Advanced Materials, Vol. 21, Issue 40
NIR-to-NIR Two-Photon Excited CaF 2 :Tm 3+ ,Yb 3+ Nanoparticles: Multifunctional Nanoprobes for Highly Penetrating Fluorescence Bio-Imaging
journal, October 2011
- Dong, Ning-Ning; Pedroni, Marco; Piccinelli, Fabio
- ACS Nano, Vol. 5, Issue 11
Seeing, Targeting and Delivering with Upconverting Nanoparticles
journal, August 2018
- Jalani, Ghulam; Tam, Vivienne; Vetrone, Fiorenzo
- Journal of the American Chemical Society, Vol. 140, Issue 35
Balancing power density based quantum yield characterization of upconverting nanoparticles for arbitrary excitation intensities
journal, January 2013
- Liu, Haichun; Xu, Can T.; Lindgren, David
- Nanoscale, Vol. 5, Issue 11
Perspectives for Upconverting Nanoparticles
journal, September 2017
- Wilhelm, Stefan
- ACS Nano, Vol. 11, Issue 11
Formation Mechanism, Structural, and Upconversion Properties of Alkaline Rare-Earth Fluoride Nanocrystals Doped With Yb 3+ /Er 3+ Ions
journal, May 2018
- Grzyb, Tomasz; Przybylska, Dominika
- Inorganic Chemistry, Vol. 57, Issue 11
Near-Infrared-Triggered Anticancer Drug Release from Upconverting Nanoparticles
journal, August 2014
- Fedoryshin, Laura L.; Tavares, Anthony J.; Petryayeva, Eleonora
- ACS Applied Materials & Interfaces, Vol. 6, Issue 16
Near-Infrared Light Photocontrolled Targeting, Bioimaging, and Chemotherapy with Caged Upconversion Nanoparticles in Vitro and in Vivo
journal, September 2013
- Chien, Yi-Hsin; Chou, Yu-Lin; Wang, Shu-Wen
- ACS Nano, Vol. 7, Issue 10
(α-NaYbF 4 :Tm 3+ )/CaF 2 Core/Shell Nanoparticles with Efficient Near-Infrared to Near-Infrared Upconversion for High-Contrast Deep Tissue Bioimaging
journal, August 2012
- Chen, Guanying; Shen, Jie; Ohulchanskyy, Tymish Y.
- ACS Nano, Vol. 6, Issue 9
Design considerations for nanotherapeutics in oncology
journal, November 2015
- Stylianopoulos, Triantafyllos; Jain, Rakesh K.
- Nanomedicine: Nanotechnology, Biology and Medicine, Vol. 11, Issue 8
Tunable Near Infrared to Ultraviolet Upconversion Luminescence Enhancement in (α-NaYF 4 :Yb,Tm)/CaF 2 Core/Shell Nanoparticles for In situ Real-time Recorded Biocompatible Photoactivation
journal, May 2013
- Shen, Jie; Chen, Guanying; Ohulchanskyy, Tymish Y.
- Small
Engineering bright sub-10-nm upconverting nanocrystals for single-molecule imaging
journal, March 2014
- Gargas, Daniel J.; Chan, Emory M.; Ostrowski, Alexis D.
- Nature Nanotechnology, Vol. 9, Issue 4
Direct Evidence of a Surface Quenching Effect on Size-Dependent Luminescence of Upconversion Nanoparticles
journal, August 2010
- Wang, Feng; Wang, Juan; Liu, Xiaogang
- Angewandte Chemie, Vol. 122, Issue 41
On-demand drug delivery from local depots
journal, December 2015
- Brudno, Yevgeny; Mooney, David J.
- Journal of Controlled Release, Vol. 219
Ion–ion interactions in β-NaGdF 4 :Yb 3+ ,Er 3+ nanocrystals – the effect of ion concentration and their clustering
journal, January 2015
- Noculak, A.; Podhorodecki, A.; Pawlik, G.
- Nanoscale, Vol. 7, Issue 32
Recent advances in the chemistry of lanthanide-doped upconversion nanocrystals
journal, January 2009
- Wang, Feng; Liu, Xiaogang
- Chemical Society Reviews, Vol. 38, Issue 4
Lanthanide-Doped LiLuF 4 Upconversion Nanoprobes for the Detection of Disease Biomarkers
journal, January 2014
- Huang, Ping; Zheng, Wei; Zhou, Shanyong
- Angewandte Chemie International Edition, Vol. 53, Issue 5
A NIR-driven photocatalyst based on α-NaYF 4 :Yb,Tm@TiO 2 core–shell structure supported on reduced graphene oxide
journal, March 2016
- Wang, Wanjun; Li, Yecheng; Kang, Zhiwen
- Applied Catalysis B: Environmental, Vol. 182
Role of titanium dioxide (TiO2) structural design/morphology in photocatalytic air purification
journal, July 2020
- Mamaghani, Alireza Haghighat; Haghighat, Fariborz; Lee, Chang-Seo
- Applied Catalysis B: Environmental, Vol. 269
Aufwärtskonvertierende NaYF 4 :Yb,Er/NaYF 4 -Kern/Schale-Nanokristalle mit hoher Lumineszenzquantenausbeute
journal, June 2018
- Homann, Christian; Krukewitt, Lisa; Frenzel, Florian
- Angewandte Chemie, Vol. 130, Issue 28
NIR-Triggered Anticancer Drug Delivery by Upconverting Nanoparticles with Integrated Azobenzene-Modified Mesoporous Silica
journal, March 2013
- Liu, Jianan; Bu, Wenbo; Pan, Limin
- Angewandte Chemie, Vol. 125, Issue 16
Visible-to-NIR Photon Harvesting: Progressive Engineering of Catalysts for Solar-Powered Environmental Purification and Fuel Production
journal, August 2018
- Yang, Min-Quan; Gao, Minmin; Hong, Minghui
- Advanced Materials, Vol. 30, Issue 47
Direct Evidence of a Surface Quenching Effect on Size-Dependent Luminescence of Upconversion Nanoparticles
journal, August 2010
- Wang, Feng; Wang, Juan; Liu, Xiaogang
- Angewandte Chemie International Edition, Vol. 49, Issue 41
Activation of the surface dark-layer to enhance upconversion in a thermal field
journal, February 2018
- Zhou, Jiajia; Wen, Shihui; Liao, Jiayan
- Nature Photonics, Vol. 12, Issue 3
Photo-Driven Expulsion of Molecules from Mesostructured Silica Nanoparticles
journal, May 2007
- Angelos, Sarah; Choi, Eunshil; Vögtle, Fritz
- The Journal of Physical Chemistry C, Vol. 111, Issue 18
Current advances in lanthanide ion (Ln 3+ )-based upconversion nanomaterials for drug delivery
journal, January 2015
- Yang, Dongmei; Ma, Ping'an; Hou, Zhiyou
- Chemical Society Reviews, Vol. 44, Issue 6
Anion-Doped TiO 2 Nanocatalysts for Water Purification under Visible Light
journal, February 2013
- Likodimos, Vlassis; Han, Changseok; Pelaez, Miguel
- Industrial & Engineering Chemistry Research, Vol. 52, Issue 39
Near-Infrared-to-Blue Upconversion in Colloidal BaYF 5 :Tm 3+ , Yb 3+ Nanocrystals
journal, May 2009
- Vetrone, Fiorenzo; Mahalingam, Venkataramanan; Capobianco, John A.
- Chemistry of Materials, Vol. 21, Issue 9